Method for performing a vapor deposition process

ABSTRACT

A method for performing a vapor deposition process is described. The vapor deposition process involves the deposition of a thin film, such as a ruthenium (Ru), rhenium (Re) or rhodium (Rh) film, on a substrate using a solid-phase or liquid-phase precursor. The method facilitates the initiation of gas lines to supply dilution gas(es), carrier gas(es) and precursor vapor to the deposition system, the pre-heating and heating of the substrate, the pre-conditioning of the film precursor vaporization system, and the flow stabilization of the carrier gas(es) and the precursor vapor, for example.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a method for thin film deposition, andmore particularly to a method for preparing a vapor deposition systemfor depositing a thin film on a substrate.

2. Description of Related Art

The introduction of copper (Cu) metal into multilayer metallizationschemes for manufacturing integrated circuits can necessitate the use ofdiffusion barriers/liners to promote adhesion and growth of the Culayers and to prevent diffusion of Cu into the dielectric materials.Barriers/liners that are deposited onto dielectric materials can includerefractive materials, such as tungsten (W), molybdenum (Mo), andtantalum (Ta), that are non-reactive and immiscible in Cu, and can offerlow electrical resistivity. Current integration schemes that integrateCu metallization and dielectric materials can require barrier/linerdeposition processes at substrate temperature between about 400° C. andabout 500° C., or lower.

For example, Cu integration schemes for technology nodes less than orequal to 130 nm can utilize a low dielectric constant (low-k)inter-level dielectric, followed by a physical vapor deposition (PVD) Talayer or a TaN/Ta layer, followed by a PVD Cu seed layer, and anelectro-chemical deposition (ECD) Cu fill. Generally, Ta layers arechosen for their adhesion properties (i.e., their ability to adhere onlow-k films), and Ta/TaN layers are generally chosen for their barrierproperties (i.e., their ability to prevent Cu diffusion into the low-kfilm).

As described above, significant effort has been devoted to the study andimplementation of thin transition metal layers as Cu diffusion barriers,these studies including such materials as chromium, tantalum, molybdenumand tungsten. Each of these materials exhibits low miscibility in Cu.More recently, other materials, such as ruthenium (Ru) and rhodium (Rh),have been identified as potential barrier layers since they are expectedto behave similarly to conventional refractory metals. However, the useof Ru or Rh can permit the use of only one barrier layer, as opposed totwo layers, such as Ta/TaN. This observation is due to the adhesive andbarrier properties of these materials. For example, one Ru layer canreplace the Ta/TaN barrier layer. Moreover, current research is findingthat the one Ru layer can further replace the Cu seed layer, and bulk Cufill can proceed directly following Ru deposition. This observation isdue to good adhesion between the Cu and the Ru layers.

Conventionally, Ru layers can be formed by thermally decomposing aruthenium-containing precursor, such as a ruthenium carbonyl precursor,in a thermal chemical vapor deposition (TCVD) process. Materialproperties of Ru layers that are deposited by thermal decomposition ofruthenium carbonyl precursors (e.g., Ru₃(CO)₁₂) can deteriorate when thesubstrate temperature is lowered to below about 400° C. As a result, anincrease in the (electrical) resistivity of the Ru layers and poorsurface morphology (e.g., the formation of nodules) at low depositiontemperatures has been attributed to increased incorporation of reactionby-products into the thermally deposited Ru layers. Both effects can beexplained by a reduced carbon monoxide (CO) desorption rate from thethermal decomposition of the ruthenium carbonyl precursor at substratetemperatures below about 400° C.

Additionally, the use of metal carbonyls, such as ruthenium carbonyl orrhenium carbonyl, can lead to poor deposition rates due to their lowvapor pressure, and the transport issues associated therewith. Overall,the inventors have observed that current deposition systems suffer fromsuch a low rate, making the deposition of such metal films impractical.Furthermore, the inventors have observed that current deposition systemssuffer from poor film uniformity.

SUMMARY OF THE INVENTION

A method is provided for preparing a deposition system for performing adeposition process to deposit a thin film on a substrate.

Further yet, a method is provided for preparing a deposition system forperforming a deposition process for depositing metal-containing filmsusing metal carbonyl precursors.

According to one embodiment, a method of, and computer readable mediumfor, depositing a thin film on a substrate is described, comprising:providing the substrate within a deposition system; providing a filmprecursor vaporization system coupled to the deposition system, andconfigured to supply a film precursor vapor to the deposition system;performing a deposition process within the deposition system to depositthe thin film on the substrate by: introducing a flow of process gascontaining the film precursor vapor and a carrier gas to the substrate,and maintaining the deposition system at a deposition pressure; andprior to performing the deposition process, performing the following:heating the substrate to a deposition temperature, stabilizing the flowof process gas at a deposition flow rate without introducing the flow ofprocess gas to the deposition system, stabilizing a system pressure inthe film precursor vaporization system without introducing the flow ofprocess gas to the deposition system, and stabilizing the substrate atthe deposition temperature without introducing the flow of process gasto the deposition system. The computer readable medium contains programinstructions for execution on the deposition system, which when executedby the deposition system, cause the deposition system to perform thesteps described above.

BRIEF DESCRIPTION OF THE DRAWINGS

In the accompanying drawings:

FIG. 1 depicts a schematic view of a deposition system according to anembodiment;

FIG. 2 depicts a schematic view of a deposition system according toanother embodiment;

FIGS. 3A through 3H depict a process flow diagram for establishing aflow of precursor vapor to a deposition system according to anembodiment;

FIG. 4 illustrates a method of depositing a thin film on a substrateaccording to an embodiment; and

FIGS. 5A through 5C schematically show, in cross-sectional views,formation of a metal layer on a patterned substrate according to anotherembodiment.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

In the following description, in order to facilitate a thoroughunderstanding of the invention and for purposes of explanation and notlimitation, specific details are set forth, such as a particulargeometry of the deposition system and descriptions of variouscomponents. However, it should be understood that the invention may bepracticed in other embodiments that depart from these specific details.

Referring now to the drawings, wherein like reference numerals designateidentical or corresponding parts throughout the several views, FIG. 1schematically illustrates a deposition system 1 for depositing a thinfilm, such as a metal film or a metal-containing film. The thin film mayinclude materials suitable for use as seed layers or barrier layers inthe metallization of inter-/intra-connect structures in electronicdevices; materials suitable for use as gate dielectrics in electronicdevices; or materials suitable for use as capacitor dielectrics in DRAMdevices. For example, the thin film may include a metal, metal oxide,metal nitride, metal oxynitride, metal silicate, metal silicide, etc.The deposition system 1 may include any vapor deposition systemconfigured to form a thin film from a film precursor vapor including,but not limited to: a chemical vapor deposition (CVD) system, aplasma-enhanced CVD (PECVD) system, an atomic layer deposition (ALD)system, a plasma-enhanced ALD (PEALD) system, etc.

According to one embodiment, a metal layer is deposited on a substratefrom a metal carbonyl precursor using a thermal chemical vapordeposition system. While other metal carbonyl precursors may be used,embodiments of the invention may henceforth be described with particularreference to ruthenium carbonyl, such as Ru₃(CO)₁₂, with theunderstanding that the invention is not so limited. The depositionsystem 1 comprises a process chamber 10 having a substrate holder 20configured to support a substrate 25, upon which the thin film, such asa metal layer, is formed. The process chamber 10 is coupled to a filmprecursor vaporization system 50 via a vapor precursor delivery system40.

The process chamber 10 is further coupled to a vacuum pumping system 38through a duct 36, wherein the vacuum pumping system 38 is configured toevacuate the process chamber 10, vapor precursor delivery system 40, andfilm precursor vaporization system 50 to a pressure suitable for formingthe metal layer on the substrate 25, and suitable for evaporation (orsublimation) of the metal carbonyl precursor 52 in the film precursorvaporization system 50.

Still referring to FIG. 1, the film precursor vaporization system 50 isconfigured to store a metal carbonyl precursor 52, to heat the metalcarbonyl precursor 52 to a temperature sufficient for vaporizing themetal carbonyl precursor 52, and to introduce metal carbonyl precursorvapor to the vapor precursor delivery system 40. The metal carbonylprecursor 52 can be solid under the selected heating conditions in thefilm precursor vaporization system 50. Alternately, the metal carbonylprecursor 52 can be a liquid. The terms “vaporization,” “sublimation”and “evaporation” are used interchangeably herein to refer to thegeneral formation of a vapor (gas) from a solid or liquid precursor,regardless of whether the transformation is, for example, from solid toliquid to gas, solid to gas, or liquid to gas. Below, the use of a solidmetal carbonyl precursor 52 is described; however, those skilled in theart will appreciate that metal carbonyl precursors that are liquidsunder the selected heating conditions can be used without departing fromthe scope of the invention. For instance, the metal carbonyl precursorcan have the general formula M_(x)(CO)_(y), and can comprise a tungstencarbonyl, a nickel carbonyl, a molybdenum carbonyl, a cobalt carbonyl, arhodium carbonyl, a rhenium carbonyl, a chromium carbonyl, a rutheniumcarbonyl, or an osmium carbonyl, or a combination of two or morethereof. These metal carbonyls include, but are not limited to, W(CO)₆,Ni(CO)₄, Mo(CO)₆, Co₂(CO)₈, Rh₄(CO)₁₂, Re₂(CO)₁₀, Cr(CO)₆, Ru₃(CO)₁₂, orOs₃(CO)₁₂, or a combination of two or more thereof.

In order to achieve the desired temperature for vaporizing the metalcarbonyl precursor 52 (e.g., subliming the solid metal carbonylprecursor 52), the film precursor vaporization system 50 is coupled to avaporization temperature control system 54 configured to control thevaporization temperature. For instance, the temperature of the metalcarbonyl precursor 52 is generally elevated to approximately 40° C. to45° C. in conventional systems in order to sublime the rutheniumcarbonyl (Ru₃(CO)₁₂). At this temperature, the vapor pressure of theRu₃(CO)₁₂, for instance, ranges from approximately 1 to approximately 3mTorr. As the metal carbonyl precursor is heated to cause evaporation(or sublimation), a carrier gas can be passed over or through the metalcarbonyl precursor 52, or any combination thereof. The carrier gas caninclude, for example, an inert gas, such as a noble gas, He, Ne, Ar, Kr,or Xe, or a combination of two or more thereof. Alternately, otherembodiments contemplate omitting the inert carrier gas. Additionally, amonoxide gas, such as carbon monoxide (CO), can be added to the inertcarrier gas. Alternately, other arrangements contemplate the monoxidegas replacing the inert carrier gas.

For example, a gas supply system 60 is coupled to the film precursorvaporization system 50, and it is configured to, for instance, supply acarrier gas, such as an inert gas, or a CO gas, or a mixture thereof,beneath the metal carbonyl precursor 52 via feed line 61, or over themetal carbonyl precursor 52 via feed line 62. In addition, or in thealternative, the gas supply system 60 is coupled to the vapor precursordelivery system 40 downstream from the film precursor vaporizationsystem 50 to supply the gas to the vapor of the metal carbonyl precursor52 via feed line 63 as or after it enters the vapor precursor deliverysystem 40.

Although not shown, the gas supply system 60 can comprise a carrier gassource, such as a CO gas source or an inert gas source or both, one ormore control valves, one or more filters, and a mass flow controller.For instance, the flow rate of the carrier gas can be between about 0.1standard cubic centimeters per minute (sccm) and about 1000 sccm.Alternately, the flow rate of the carrier gas can be between about 10sccm and about 500 sccm. Still alternately, the flow rate of the carriergas can be between about 50 sccm and about 200 sccm.

Downstream from the film precursor vaporization system 50, the metalprecursor vapor flows with the carrier gas through the vapor precursordelivery system 40 until it enters a vapor distribution system 30coupled to or within the process chamber 10. The vapor precursordelivery system 40 can be coupled to a vapor line temperature controlsystem 42 in order to control the vapor line temperature and preventdecomposition of the film precursor vapor as well as condensation of thefilm precursor vapor. For example, the vapor line temperature can be setto a value approximately equal to or greater than the vaporizationtemperature. Additionally, for example, the vapor precursor deliverysystem 40 can be characterized by a high conductance in excess of about50 liters/second.

Referring again to FIG. 1, the vapor distribution system 30, coupled tothe process chamber 10, comprises a vapor distribution plenum 32 withinwhich the vapor disperses prior to passing through a vapor distributionplate 34 and entering a processing zone 33 above substrate 25. Inaddition, the vapor distribution plate 34 can be coupled to adistribution plate temperature control system 35 configured to controlthe temperature of the vapor distribution plate 34. For example, thetemperature of the vapor distribution plate can be set to a valueapproximately equal to the vapor line temperature. However, it may beless, or it may be greater.

Additionally, a dilution gas source 37 may optionally be coupled to theprocess chamber 10 and/or vapor distribution system 30 and may beconfigured to add a dilution gas to dilute the process gas containingthe metal carbonyl precursor vapor and the carrier gas. As shown in FIG.1, the dilution gas source 37 can be coupled to the vapor distributionsystem 30 via feed line 37 a and configured to add the dilution gas tothe process gas in the vapor distribution plenum 32 before the processgas passes through the vapor distribution plate 34 into the processingzone 33. Alternately, the dilution gas source 37 can be coupled to theprocess chamber 10 via feed line 37 b and configured to add the dilutiongas to the process gas in the processing zone 33 above the substrate 25after the process gas passes through the vapor distribution plate 34.Still alternately, the dilution gas source 37 can be coupled to thevapor distribution system 30 via feed line 37 c and configured to addthe dilution gas to the process gas in the vapor distribution plate 34.As will be appreciated by those skilled in the art, the dilution gas canbe added to the process gas at other locations in the vapor distributionsystem 30 and the process chamber 10 without departing from the scope ofthe invention.

Additionally yet, the dilution gas is introduced to the process gas fromthe dilution gas source 37 through one of feed lines 37 a, 37 b, 37 c,or other feed lines (not shown) in such a way that the concentration ofdilution gas at one region above substrate 25 can be adjusted to bedifferent than the concentration of dilution gas at another region abovesubstrate 25. For example, the flow of dilution gas to a central regionof substrate 25 can be different than the flow of dilution gas to aperipheral region of substrate 25.

Once film precursor vapor enters the processing zone 33, the filmprecursor vapor thermally decomposes upon adsorption at the substratesurface due to the elevated temperature of the substrate 25, and thethin film is formed on the substrate 25. The substrate holder 20 isconfigured to elevate the temperature of substrate 25 by virtue of thesubstrate holder 20 being coupled to a substrate temperature controlsystem 22. For example, the substrate temperature control system 22 canbe configured to elevate the temperature of substrate 25 up toapproximately 500° C. In one embodiment, the substrate temperature canrange from about 100° C. to about 500° C. In another embodiment, thesubstrate temperature can range from about 150° C. to about 350° C.Additionally, process chamber 10 can be coupled to a chamber temperaturecontrol system 12 configured to control the temperature of the chamberwalls.

As described above, for example, conventional systems have contemplatedoperating the film precursor vaporization system 50, as well as thevapor precursor delivery system 40, within a temperature range ofapproximately 40-45° C. for ruthenium carbonyl in order to limit metalvapor precursor decomposition and metal vapor precursor condensation.For example, the ruthenium carbonyl precursor can decompose at elevatedtemperatures to form by-products, such as those illustrated below:

Ru₃(CO)₁₂*(ad)

Ru₃(CO)_(x)*(ad)+(12−x)CO(g)  (1)

or,

Ru₃(CO)_(x)(ad)

3Ru(s)+xCO(g)  (2)

wherein these by-products can adsorb (ad), i.e., condense, on theinterior surfaces of the deposition system 1. The accumulation ofmaterial on these surfaces can cause problems from one substrate to thenext, such as process repeatability. Alternatively, for example, theruthenium carbonyl precursor can condense at depressed temperatures tocause recrystallization, viz.

Ru₃(CO)₁₂(g)

Ru₃(CO)₁₂*(ad)  (3).

In summary, the low vapor pressure of some metal carbonyl precursors(e.g., Ru₃(CO)₁₂) and the small process window result in a very lowdeposition rate of a metal layer on the substrate 25.

Adding a CO gas as a carrier gas to the metal carbonyl precursor vaporcan reduce the above-mentioned problems that limit the delivery of themetal carbonyl precursor to the substrate. Thus, according to anembodiment, the CO gas is added to the metal carbonyl precursor vapor toreduce dissociation of the metal carbonyl precursor vapor in the gasline, thereby shifting the equilibrium in Equation (1) to the left andreducing premature decomposition of the metal carbonyl precursor in thevapor precursor delivery system 40 prior to delivery of the metalcarbonyl precursor to the process chamber 10. It is believed thataddition of the CO gas to the metal carbonyl precursor vapor allows forincreasing the vaporization temperature from approximately 40° C. toapproximately 150° C., or higher. The elevated temperature increases thevapor pressure of the metal carbonyl precursor, resulting in increaseddelivery of the metal carbonyl precursor to the process chamber and,hence, increased deposition rate of the metal on the substrate 25.Furthermore, it has been visually observed that flowing a mixture of aninert gas, such as Ar, and the CO gas over or through the metal carbonylprecursor reduces premature decomposition of the metal carbonylprecursor.

Accordingly, the addition of CO gas to a Ru₃(CO)₁₂ precursor vaporallows for maintaining the Ru₃(CO)₁₂ precursor vaporization temperaturefrom approximately 40° C. to approximately 150° C. Alternately, thevaporization temperature can be maintained at approximately 60° C. toapproximately 90° C.

Thermal decomposition of metal carbonyl precursors and subsequent metaldeposition on the substrate 25 is thought to proceed predominantly by COelimination and desorption of CO by-products from the substrate 25.Incorporation of CO by-products into the metal layers during depositioncan result from incomplete decomposition of the metal carbonylprecursor, incomplete removal of CO by-products from the metal layer,and re-adsorption of CO by-products from the process chamber 10 onto themetal layer.

It is believed that CO incorporation into a metal layer duringdeposition leads to surface roughness in the form of nodules in themetal layer, where the growth of nodules is enhanced by increasedincorporation of CO by-products into the metal layer. The number ofnodules is expected to increase as the thickness of the metal layerincreases. Furthermore, the incorporation of CO by-products into themetal layer increases the resistivity of the metal layer.

Incorporation of CO by-products into the metal layer can be reduced by(1) lowering the process pressure, and (2) increasing the substratetemperature. The above-mentioned problems can also be reduced by addinga dilution gas in the process chamber 10 to the process gas containingthe metal carbonyl precursor vapor and the CO gas for controlling andreducing the partial pressure of by-products and the CO gas in theprocess chamber. Thus, according to an embodiment of the invention, adilution gas from dilution gas source 37 is added to the process gas forcontrolling and reducing the partial pressure of CO by-products on themetal layer and the partial pressure of CO in the process chamber 10,thereby forming a smooth metal layer. The dilution gas can include, forexample, an inert gas, such as a noble gas, He, Ne, Ar, Kr, or Xe, or amixture of two or more thereof. The dilution gas may further contain areducing gas to improve the material properties of the metal layer, forexample the electrical resistivity. The reducing gas can, for example,contain H₂, a silicon-containing gas (e.g., SiH₄, Si₂H₆, or SiCl₂H₂), aboron-containing gas (e.g., BH₃, B₂H₆, or B₃H₉), or anitrogen-containing gas (e.g., NH₃). According to an embodiment of theinvention, the process chamber pressure can be between about 0.1 mTorrand about 200 mTorr. Alternately, the process chamber pressure can bebetween about 1 mTorr and about 200 mTorr. Still alternately, theprocess chamber pressure can be between about 10 mTorr and about 200mTorr.

Since the addition of the CO gas to the metal carbonyl precursor vaporincreases the thermal stability of the metal carbonyl precursor vapor,the relative concentration of the metal carbonyl precursor vapor to theCO gas in the process gas can be utilized to control the decompositionrate of the metal carbonyl precursor on the substrate 25 at a certainsubstrate temperature. Furthermore, the substrate temperature can beutilized to control the decomposition rate (and thereby the depositionrate) of the metal on the substrate 25. As those skilled in the art willreadily appreciate, the amount of CO gas and the substrate temperaturecan easily be varied to allow for a desired vaporization temperature ofthe metal carbonyl precursor and for achieving a desired deposition rateof the metal carbonyl precursor on the substrate 25.

Furthermore, the amount of CO gas in the process gas can be selected sothat metal deposition on the substrate 25 from a metal carbonylprecursor occurs in a kinetic-limited temperature regime. For example,the amount of CO gas in the process gas can be increased until the metaldeposition process is observed to occur in a kinetic-limited temperatureregime. A kinetic-limited temperature regime refers to the range ofdeposition conditions where the deposition rate of a chemical vapordeposition process is limited by the kinetics of the chemical reactionsat the substrate surface, typically characterized by a strong dependenceof deposition rate on temperature. Unlike the kinetic-limitedtemperature regime, a mass-transfer limited regime is normally observedat higher substrate temperatures and includes a range of depositionconditions where the deposition rate is limited by the flux of chemicalreactants to the substrate surface. A mass-transfer limited regime ischaracterized by a strong dependence of deposition rate on metalcarbonyl precursor flow rate and is independent of depositiontemperature. Metal deposition in the kinetic-limited regime normallyresults in good step coverage and good conformality of the metal layeron patterned substrates. Conformality is commonly defined as thethinnest part of the metal layer on the sidewall of a feature on thepatterned substrate divided by the thickest part of the metal layer onthe sidewall. Step coverage is commonly defined as the sidewall coverage(metal layer thickness on sidewall divided by the metal layer thicknessaway from the feature) divided by the bottom coverage (metal layerthickness on the bottom of the feature divided by the metal layerthickness away from the feature).

Additionally, in accordance with the present invention, it is observedthat the stability of film deposition and the resultant properties ofthe deposited film can be affected by variations in the flow of CO gasand precursor vapor to the deposition system. For example, during theinitial introduction of CO gas and precursor vapor to the depositionsystem, flow variations may occur until the flow rate stabilizes throughthe metal precursor vaporization system, the vapor delivery system, andthe vapor distribution system. According to one embodiment, as will bedescribed later, a sequence of process steps are performed prior to thedeposition process in order to, for example stabilize system conditions.

Still referring to FIG. 1, optionally, the deposition system 1 can beperiodically cleaned using an in-situ cleaning system 70 coupled to, forexample, the vapor precursor delivery system 40, as shown in FIG. 1. Pera frequency determined by the operator, the in-situ cleaning system 70can perform routine cleanings of the deposition system 1 in order toremove accumulated residue on internal surfaces of deposition system 1.The in-situ cleaning system 70 can, for example, comprise a radicalgenerator configured to introduce chemical radical capable of chemicallyreacting and removing such residue. Additionally, for example, thein-situ cleaning system 70 can, for example, include an ozone generatorconfigured to introduce a partial pressure of ozone. For instance, theradical generator can include an upstream plasma source configured togenerate oxygen or fluorine radical from oxygen (O₂), nitrogentrifluoride (NF₃), O₃, XeF₂, ClF₃, or C₃F₈ (or, more generally,C_(x)F_(y)), respectively. The radical generator can include an ASTRON®reactive gas generator, commercially available from MKS Instruments,Inc., ASTeX® Products (90 Industrial Way, Wilmington, Mass. 01887).

Still referring the FIG. 1, the deposition system 1 can further includea control system 80 configured to operate and control the operation ofthe deposition system 1. The control system 80 is coupled to the processchamber 10, the substrate holder 20, the substrate temperature controlsystem 22, the chamber temperature control system 12, the vapordistribution system 30, the vapor precursor delivery system 40, the filmprecursor vaporization system 50, the carrier gas supply system 60, thedilution gas source 37, and the optional in-situ cleaning system 70.

In another embodiment, FIG. 2 illustrates a deposition system 100 fordepositing a metal film, such as a ruthenium (Ru) film, on a substrate.The deposition system 100 comprises a process chamber 110 having asubstrate holder 120 configured to support a substrate 125 upon whichthe metal layer is formed. The process chamber 110 is coupled to aprecursor delivery system 105 having film precursor vaporization system150 configured to store and evaporate a metal carbonyl precursor 152,and a vapor precursor delivery system 140 configured to transport themetal carbonyl precursor 152 to the process chamber 110.

The process chamber 110 comprises an upper chamber section 111, a lowerchamber section 112, and an exhaust chamber 113. An opening 114 isformed within lower chamber section 112, where lower chamber section 112couples with exhaust chamber 113.

Referring still to FIG. 2, substrate holder 120 provides a horizontalsurface to support substrate (or wafer) 125, which is to be processed.The substrate holder 120 can be supported by a cylindrical supportmember 122, which extends upward from the lower portion of exhaustchamber 113. A shield ring 124 for reducing CO poisoning on thesubstrate 125 on the substrate holder 120 is provided on the edge ofsubstrate holder 120. Furthermore, the substrate holder 120 comprises aheater 126 coupled to substrate holder temperature control system 128.The heater 126 can, for example, include one or more resistive heatingelements. Alternately, the heater 126 can, for example, include aradiant heating system, such as a tungsten-halogen lamp. The substrateholder temperature control system 128 can include a power source forproviding power to the one or more heating elements, one or moretemperature sensors for measuring the substrate temperature or thesubstrate holder temperature, or both, and a controller configured toperform at least one of monitoring, adjusting, or controlling thetemperature of the substrate 125 or substrate holder 120.

During processing, the heated substrate 125 can thermally decompose themetal carbonyl precursor vapor, and enable deposition of a metal layeron the substrate 125. According to an embodiment, the metal carbonylprecursor 152 can be a ruthenium carbonyl precursor, for exampleRu₃(CO)₁₂. As will be appreciated by those skilled in the art of thermalchemical vapor deposition, other metal carbonyl precursors and otherruthenium carbonyl precursors can be used without departing from thescope of the invention. The substrate holder 120 is heated to apre-determined temperature that is suitable for depositing the desiredRu metal layer or other metal layer onto the substrate 125.Additionally, a heater (not shown) coupled to a chamber temperaturecontrol system 121 can be embedded in the walls of process chamber 110to heat the chamber walls to a pre-determined temperature. The heatercan maintain the temperature of the walls of process chamber 110 fromabout 40° C. to about 150° C., or from about 40° C. to about 80° C. Apressure gauge (not shown) is used to measure the process chamberpressure. According to an embodiment of the invention, the processchamber pressure can be between about 0.1 mTorr and about 200 mTorr.Alternately, the process chamber pressure can be between about 1 mTorrand about 100 mTorr. Still alternately, the process chamber pressure canbe between about 2 mTorr and about 50 mTorr.

Also shown in FIG. 2, a vapor distribution system 130 is coupled to theupper chamber section 111 of process chamber 110. Vapor distributionsystem 130 comprises a vapor distribution plate 131 configured tointroduce precursor vapor from vapor distribution plenum 132 to aprocessing zone 133 above substrate 125 through one or more orifices134.

According to an embodiment of the invention, a dilution gas source 137is coupled to the process chamber 110 and is configured to add adilution gas to dilute the process gas containing the metal carbonylprecursor vapor and the CO gas using feed lines 137 a, 137 b, and/or 137c, valves 197, one or more filters (not shown), and a mass flowcontroller (not shown). As shown in FIG. 2, the dilution gas source 137can be coupled to the vapor distribution system 130 of process chamber110 and is configured to add the dilution gas to the process gas in thevapor distribution plenum 132 via feed line 137 a before the process gaspasses through the vapor distribution plate 131 into the processing zone133 above the substrate 125, or the dilution gas source 137 can beconfigured to add the dilution gas to the process gas inside the vapordistribution plate 131 via feed line 137 c. Alternately, the dilutiongas source 137 can be coupled to the process chamber 110 and isconfigured to add the dilution gas to the process gas in the processingzone 133 via feed line 137 b after the process gas passes through thevapor distribution plate 131. As will be appreciated by those skilled inthe art, the dilution gas can be added to the process gas at otherlocations in the process chamber 110 without departing from the scope ofthe invention.

In yet another embodiment, the dilution gas is introduced to the processgas from the dilution gas source 137 through one of feed lines 137 a,137 b, 137 c, or other feed lines (not shown) in such a way that theconcentration of dilution gas at one region above substrate 125 can beadjusted to be different than the concentration of dilution gas atanother region above substrate 125. For example, the flow of dilutiongas to a central region of substrate 125 can be different than the flowof dilution gas to a peripheral region of substrate 125.

Furthermore, an opening 135 is provided in the upper chamber section 111for introducing a metal carbonyl precursor vapor from vapor precursordelivery system 140 into vapor distribution plenum 132. Moreover,temperature control elements 136, such as concentric fluid channelsconfigured to flow a cooled or heated fluid, are provided forcontrolling the temperature of the vapor distribution system 130, andthereby prevent the decomposition or condensation of the metal carbonylprecursor inside the vapor distribution system 130. For instance, afluid, such as water, can be supplied to the fluid channels from a vapordistribution temperature control system 138. The vapor distributiontemperature control system 138 can include a fluid source, a heatexchanger, one or more temperature sensors for measuring the fluidtemperature or vapor distribution plate temperature or both, and acontroller configured to control the temperature of the vapordistribution plate 131 from about 20° C. to about 150° C.

As illustrated in FIG. 2, a film precursor vaporization system 150 isconfigured to hold a metal carbonyl precursor 152 and evaporate (orsublime) the metal carbonyl precursor 152 by elevating the temperatureof the metal carbonyl precursor. A precursor heater 154 is provided forheating the metal carbonyl precursor 152 to maintain the metal carbonylprecursor 152 at a temperature that produces a desired vapor pressure ofmetal carbonyl precursor 152. The precursor heater 154 is coupled to avaporization temperature control system 156 configured to control thetemperature of the metal carbonyl precursor 152. For example, theprecursor heater 154 can be configured to adjust the temperature of themetal carbonyl precursor 152 from about 40° C. to about 150° C., or fromabout 60° C. to about 90° C.

As the metal carbonyl precursor 152 is heated to cause evaporation (orsublimation), a carrier gas can be passed over or through the metalcarbonyl precursor 152, or any combination thereof. The carrier gas caninclude, for example, an inert gas, such as a noble gas (i.e., He, Ne,Ar, Kr, Xe). Alternately, other embodiments contemplate omitting theinert carrier gas. According to an embodiment of the invention, a CO gascan be added to the inert carrier gas. Alternately, other embodimentscontemplate the CO gas replacing the inert carrier gas. For example, agas supply system 160 is coupled to the film precursor vaporizationsystem 150, and it is configured to, for instance, flow the carrier gas,the CO gas, or both, over or through the metal carbonyl precursor 152.Although not shown in FIG. 2, gas supply system 160 can also oralternatively be coupled to the vapor precursor delivery system 140 tosupply the CO gas and optional inert carrier gas to the vapor of themetal carbonyl precursor 152 as or after it enters the vapor precursordelivery system 140. The gas supply system 160 can comprise a gas source161 containing an inert carrier gas, a CO gas, or a mixture thereof, oneor more control valves 162, one or more filters 164, and a mass flowcontroller 165. For instance, the mass flow rate of inert carrier gas orthe CO gas can range from approximately 0.1 sccm to approximately 1000sccm.

Additionally, a sensor 166 is provided for measuring the total gas flowfrom the film precursor vaporization system 150. The sensor 166 can, forexample, comprise a mass flow controller, and the amount of metalcarbonyl precursor vapor delivered to the process chamber 110 can bedetermined using sensor 166 and mass flow controller 165. Alternately,the sensor 166 can comprise a light absorption sensor to measure theconcentration of the metal carbonyl precursor in the gas flow to theprocess chamber 110.

A bypass line 167 can be located downstream from sensor 166, and it canconnect the vapor precursor delivery system 140 to an exhaust line 116.Bypass line 167 is provided for evacuating the vapor precursor deliverysystem 140, and for stabilizing the supply of the metal carbonylprecursor to the process chamber 110. In addition, a bypass valve 168,located downstream from the branching of the vapor precursor deliverysystem 140, is provided on bypass line 167.

Referring still to FIG. 2, the vapor precursor delivery system 140comprises a high conductance vapor line having first and second valves141 and 142, respectively. Additionally, the vapor precursor deliverysystem 140 can further comprise a vapor line temperature control system143 configured to heat the vapor precursor delivery system 140 viaheaters (not shown). The temperatures of the vapor lines can becontrolled to avoid condensation of the metal carbonyl precursor vaporin the vapor line. The temperature of the vapor lines can be controlledfrom about 20° C. to about 100° C., or from about 40° C. to about 90° C.

Moreover, a CO gas can be supplied from a gas supply system 190. Forexample, the gas supply system 190 is coupled to the vapor precursordelivery system 140, and it is configured to, for instance, mix the COgas with the metal carbonyl precursor vapor in the vapor precursordelivery system, for example, downstream of valve 141. The gas supplysystem 190 can comprise a CO gas source 191, one or more control valves192, one or more filters 194, and a mass flow controller 195. Forinstance, the mass flow rate of CO gas can range from approximately 0.1sccm to approximately 1000 sccm.

Mass flow controllers 165 and 195, and valves 162, 192, 168, 141, and142 are controlled by controller 196, which controls the supply,shutoff, and the flow of the inert carrier gas, the CO gas, and themetal carbonyl precursor vapor. Sensor 166 is also connected tocontroller 196 and, based on output of the sensor 166, controller 196can control the carrier gas flow through mass flow controller 165 toobtain the desired metal carbonyl precursor flow to the process chamber110.

Furthermore, as described above, and as shown in FIG. 2, an optionalin-situ cleaning system 170 is coupled to the precursor delivery system105 of deposition system 100 through cleaning valve 172. For instance,the in-situ cleaning system 170 can be coupled to the vapor precursordelivery system 140. The in-situ cleaning system 170 can, for example,comprise a radical generator configured to introduce chemical radicalcapable of chemically reacting and removing such residue. Additionally,for example, the in-situ cleaning system 170 can, for example, includean ozone generator configured to introduce a partial pressure of ozone.For instance, the radical generator can include an upstream plasmasource configured to generate oxygen or fluorine radical from oxygen(O₂), nitrogen trifluoride (NF₃), ClF₃, O₃, XeF₂, or C₃F₈ (or, moregenerally, C_(x)F_(y)), respectively. The radical generator can includean ASTRON® reactive gas generator, commercially available from MKSInstruments, Inc., ASTeX® Products (90 Industrial Way, Wilmington, Mass.01887).

As illustrated in FIG. 2, the exhaust line 116 connects exhaust chamber113 to vacuum pumping system 118. A vacuum pump 119 is used to evacuateprocess chamber 110 to the desired degree of vacuum, and to removegaseous species from the process chamber 110 during processing. Anautomatic pressure controller (APC) 115 and a trap 117 can be used inseries with the vacuum pump 119. The vacuum pump 119 can include aturbo-molecular pump (TMP) capable of a pumping speed up to 500 litersper second (and greater). Alternately, the vacuum pump 119 can include adry roughing pump. During processing, the process gas can be introducedinto the process chamber 110, and the chamber pressure can be adjustedby the APC 115. The APC 115 can comprise a butterfly-type valve or agate valve. The trap 117 can collect unreacted metal carbonyl precursormaterial and by-products from the process chamber 110.

Referring back to the substrate holder 120 in the process chamber 110,as shown in FIG. 2, three substrate lift pins 127 (only two are shown)are provided for holding, raising, and lowering the substrate 125. Thesubstrate lift pins 127 are coupled to plate 123, and can be lowered tobelow to the upper surface of substrate holder 120. A drive mechanism129 utilizing, for example, an air cylinder provides means for raisingand lowering the plate 123. Substrate 125 can be transferred into andout of process chamber 110 through gate valve 200 and chamberfeed-through passage 202 via a robotic transfer system (not shown), andreceived by the substrate lift pins 127. Once the substrate 125 isreceived from the transfer system, it can be lowered to the uppersurface of the substrate holder 120 by lowering the substrate lift pins127.

Referring again to FIG. 2, a controller 180 includes a microprocessor, amemory, and a digital I/O port capable of generating control voltagessufficient to communicate and activate inputs of the deposition system100 as well as monitor outputs from the deposition system 100. Moreover,the controller 180 is coupled to and exchanges information with processchamber 110; precursor delivery system 105, which includes controller196, vapor line temperature control system 143, film precursorvaporization system 150, gas supply system 190, gas supply system 160,and vaporization temperature control system 156; vapor distributiontemperature control system 138; dilution gas source 137; vacuum pumpingsystem 118; and substrate holder temperature control system 128. In thevacuum pumping system 118, the controller 180 is coupled to andexchanges information with the automatic pressure controller 115 forcontrolling the pressure in the process chamber 110. A program stored inthe memory is utilized to control the aforementioned components ofdeposition system 100 according to a stored process recipe. One exampleof controller 180 is a DELL PRECISION WORKSTATION 610®, available fromDell Corporation, Dallas, Tex. The controller 180 may also beimplemented as a general-purpose computer, digital signal process, etc.

Controller 180 may be locally located relative to the deposition system100, or it may be remotely located relative to the deposition system 100via the internet or an intranet. Thus, controller 180 can exchange datawith the deposition system 100 using at least one of a directconnection, an intranet, or the internet. Controller 180 may be coupledto an intranet at a customer site (i.e., a device maker, etc.), orcoupled to an intranet at a vendor site (i.e., an equipmentmanufacturer). Furthermore, another computer (i.e., controller, server,etc.) can access controller 180 to exchange data via at least one of adirect connection, an intranet, or the internet.

As described above, it is observed that the stability of film depositionand the resultant properties of the deposited film can be affected byvariations in process conditions within the deposition system.Variations of pressure, precursor vapor flow rate, carrier gas flowrate, substrate temperature, etc. are examples of various processconditions that may influence the stability and repeatability of filmproperties.

According to one example, during the initial introduction of CO gas andprecursor vapor to the deposition system, flow variations may occurwhile the flow rate stabilizes through the film precursor vaporizationsystem, the vapor delivery system, and the vapor distribution system.The inventor has observed that these flow variations can affect filmproperties and the repeatability of film properties. Therefore, it isdesirable to stabilize the flow rate of precursor vapor and carrier gasprior to initiating the deposition process.

According to another example, when initiating the flow of carrier gasthrough the film precursor vaporization system, sudden changes inpressure during the initial stages of flowing gas through the precursorvaporization system can cause variations in flow conditions andincreased particle contamination. The inventor has observed that thesepressure variations can affect film properties and the repeatability offilm properties. Therefore, it is desirable to stabilize the pressurewithin the film precursor vaporization system prior to initiating thedeposition process.

According to yet another example, when heating the substrate to thedeposition temperature prior to the deposition process, the chamberenvironment within the deposition system, such as pressure, gascomposition, etc., may be different than the chamber environment for thedeposition process. The inventor has observed that a change from aninert gas environment, such as an argon environment, to a CO gasenvironment can affect the temperature stability of the substrate,which, in turn, can affect film properties and the repeatability of filmproperties. Therefore, it is desirable to stabilize the temperature ofthe substrate prior to initiating the deposition process.

Referring now to FIGS. 3A through 3H, a vapor supply system 305 forintroducing a film precursor vapor, derived from a film precursor 352contained within a film precursor vaporization system 350, to adeposition system 310 is described. Furthermore, a method of initiatinga deposition process to be performed within the deposition system 310 isillustrated in FIG. 4. The method comprises a flow chart 500 depicting asequence of process steps that are performed prior to the depositionprocess according to an embodiment. For example, the deposition processis performed according to a deposition process condition that mayinclude: operating at a pre-determined flow rate of carrier gas,operating at a pre-determined flow rate of film precursor vapor,operating at a pre-determined chamber pressure within the depositionsystem, operating at a pre-determined substrate temperature, etc.

As shown in FIG. 4, in step 510, a substrate is provided in a processspace of the deposition system 310. For example, the deposition system310 can include the depositions systems 1 or 100 described above inFIGS. 1 and 2. The substrate can, for example, be a silicon (Si)substrate. A Si substrate can be of n- or p-type, depending on the typeof device being formed. The substrate can be of any size, for example a200 mm substrate, a 300 mm substrate, or an even larger substrate.According to an embodiment of the invention, the substrate can be apatterned substrate containing one or more vias or trenches, orcombinations thereof.

As illustrated in FIG. 3A and FIG. 4 in step 520, a flow of carrier gas380 from a gas supply system 360 is initiated and stabilized through aby-pass gas line 367 to an exhaust system 318 when control valve 368 isopen. The exhaust system 318 may be independent from the evacuationsystem coupled to the deposition system 310, or it may be the same. Theflow of carrier gas 380 to the exhaust system 318 is performed torelease any accumulation of pressure within the gas supply system 360and it is performed for a period of time sufficiently long to stabilizethe flow rate of carrier gas at, for example, a flow rate consistentwith the deposition process conditions (i.e., a deposition conditionflow rate). The period of time may range from approximately 1 toapproximately 30 seconds and, desirably, the period of time may rangefrom approximately 1 to approximately 10 seconds; for instance,approximately 3 seconds.

Additionally, in step 530, a flow of purge gas 385 from gas supplysystem 360 is initiated and stabilized through a purge gas line 370 tothe deposition system 310 when control valve 372 is open. The flow ofpurge gas 385 facilitates the release of any pressure accumulation inthe purge gas line 370 and the gas supply system 360.

During this time, the chamber pressure is not controlled, e.g., maximumpumping speed is delivered to the deposition system 310. Furthermore, instep 540, while the substrate holder (or substrate pedestal) is raisedto an elevated temperature (above room temperature and at or near thedeposition condition temperature), the substrate rests on lift pins inclose proximity of the upper surface of the substrate holder in order topre-heat the substrate prior to making direct thermal contact betweenthe relatively cold substrate and the relatively hot substrate holder.In doing so, the risk of damaging the substrate due to thermal shock isreduced. The spacing between the substrate and the substrate holder mayrange from approximately 1 mm to approximately 20 mm and, desirably, thespacing may range from approximately 1 mm to approximately 10 mm; forinstance, approximately 5 mm. During this time, no film depositionoccurs, i.e., carrier gas with precursor vapor does not flow to thedeposition system 310 by virtue of control valve 342 in vapor deliveryline 340 being in a closed position.

The gas supply system 360 can comprise a first gas source 361 configuredto introduce a first inert gas, such as a noble gas (e.g., argon),through a flow valve 375 downstream of the film precursor vaporizationsystem 350, and a second gas source 362 configured to introduce a secondinert gas, such as a noble gas (e.g., argon), through another flow valve373 upstream of the film precursor vaporization system 350.Additionally, the gas supply system 360 can comprise a third gas source363 configured to introduce a monoxide gas, such as carbon monoxide(CO), through yet another flow valve 374 upstream of the film precursorvaporization system 350. Furthermore, the gas supply system 360 cancomprise a fourth gas source 364 configured to introduce an inert gas,such as a noble gas (e.g., argon), through the purge gas line 370 to thedeposition system 310. Although exemplary gases are provided above forgas sources 361, 362, 363 and 364, each gas source may supply othergases as would understood by one skilled in the art of processengineering for electronic device manufacturing. Additionally, asprovided above, the gas supply system 360 can include a carrier gassource, a carbon monoxide (CO) gas source, a purge gas source, one ormore control valves, one or more filters, one or more flow conditioningdevices, and one or more mass flow controllers for introducing variousflows, as described above and below, to deposition system 310.

For example, as illustrated in FIG. 3A, the flow of carrier gas toexhaust system 318 can include a flow of inert gas from the first gassource 361 through flow valve 375 (when open), and a flow of carbonmonoxide (CO) from the third gas source 363 through flow valve 374 (whenopen) and through a by-pass valve 377 (when open) that by-passes thefilm precursor vaporization system 350. Entry valve 376 to the filmprecursor vaporization system 350 and exit valve 378 out of the filmprecursor vaporization system 350 are thus closed when by-pass valve 377is open.

As illustrated in FIG. 3B and FIG. 4 in step 550, the substrate isheated while in contact with the substrate holder. The flow of purge gas385 from gas supply system 360 is continued through the purge gas line370 to the deposition system 310 when control valve 372 is open.Additionally, the substrate is lowered to the upper surface of thesubstrate holder, whereby thermal contact is made, and the substrate isheated to the deposition condition temperature (i.e., a temperaturedetermined for the deposition process conditions). During this time, nofilm deposition occurs, i.e., carrier gas with precursor vapor does notflow to the deposition system 310 by virtue of control valve 342 invapor delivery line 340 remaining in the closed position. The flow ofcarrier gas 380 to the exhaust system 318 may be discontinued duringstep 550 (e.g., valves 368, 374, 375 and 377 are closed).

As illustrated in FIG. 3C and FIG. 4 in step 560, the substrate isheated at an elevated pressure within the deposition system 310. Theflow of purge gas 385 from gas supply system 360 is continued throughthe purge gas line 370 to the deposition system 310 when control valve372 is open, while heating of the substrate also continues. Yet, thechamber pressure is controlled at a relatively high pressure in order toassist the conduction of heat from the substrate holder to thesubstrate. The chamber pressure may range from approximately 0.1 Torr toapproximately 1000 Torr and, desirably, the chamber pressure may rangefrom approximately 1 Torr to approximately 10 Torr; for instance,approximately 2 Torr.

Additionally, as illustrated in FIG. 3C and FIG. 4 in step 570, the flowrate of carrier gas and film precursor vapor is stabilized at thedeposition condition flow rate. To that end, a flow of carrier gas isestablished through the film precursor vaporization system 350 and thefilm precursor 352 within the film precursor vaporization system 350 isheated. The carrier gas can, for example, include carbon monoxide (CO)that is supplied from the third gas source 363 through flow valve 374(when open). The carrier gas enters the film precursor vaporizationsystem 350 through entry valve 376 when this valve is open and theby-pass valve 377 is closed. As described earlier, the film precursor352 can comprise a metal carbonyl, such as solid ruthenium carbonyl(Ru₃(CO)₁₂), which sublimes to form precursor vapor that is entrained bythe carrier gas. A flow of carrier gas and film precursor vapor 381exits the film precursor vaporization system 350 through exit valve 378(when open) and continues through the by-pass gas line 367 to theexhaust system 318 when control valve 368 is opened.

The flow of carrier gas and film precursor vapor 381 to the exhaustsystem 318 is performed for a period of time sufficiently long tostabilize the flow rate of carrier gas and film precursor vapor at, forexample, a flow rate consistent with the deposition process conditions(i.e., the deposition condition flow rate). The period of time may rangefrom approximately 1 to approximately 60 seconds and, desirably, theperiod of time may range from approximately 10 to approximately 30seconds; for instance, approximately 20 seconds. During this time, thesubstrate in the deposition system 310 is heated and no film depositionoccurs, i.e., carrier gas and precursor vapor does not flow to thedeposition system 310 by virtue of control valve 342 in vapor deliveryline 340 remaining in the closed position.

As illustrated in FIG. 3D and FIG. 4 in step 580, the gas pressurewithin the film precursor vaporization system 350 is stabilized. Theflow of purge gas 385 from gas supply system 360 is continued throughthe purge gas line 370 to the deposition system 310 when control valve372 is open, while heating of the substrate to the depositiontemperature continues and the chamber pressure is controlled at arelatively high pressure. Additionally, a flow of carrier gas throughthe film precursor vaporization system 350 continues, but the flow rateof carrier gas is altered in order to establish a gas pressure withinthe film precursor vaporization system 350 and a resulting flow ofcarrier gas and precursor vapor 382 to the exhaust system 318 at a flowrate that would be consistent with a flow of carrier gas and filmprecursor vapor to the deposition system 310 through vapor delivery line340 coupled to the deposition system 310 at the deposition conditionflow rate.

For a given mass flow rate through either the vapor delivery line 340 orthe by-pass gas line 367, a difference in the respective flowconductance (C) of each flow path or the pumping speed (S) delivered toan outlet of each flow path or a combination thereof may causevariations in the pressure upstream of each flow path in, for instance,the film precursor vaporization system 350. For a gaseous flow between afirst location at pressure P₂ and a second location at pressure P₁, theratio of the change in pressure (ΔP=P₂−P₁) along each flow path to thepressure at the second location (P₁), for instance, is related to theratio of the pumping speed at the second location (S₁) to the flowconductance (C₁₂) along the flow path, i.e., ΔP/P₁˜S₁/C₁₂.

For example, if the flow conductance of the by-pass gas line 367 to theexhaust system 318 is less than the flow conductance of the vapordelivery line 340 to the deposition system 310, the flow rate of carriergas is reduced in order to adjust the gas pressure in the film precursorvaporization system 350 to a gas pressure consistent with the flow ofcarrier gas and film precursor vapor to the deposition system 310 at thedeposition condition flow rate. Alternatively, if the flow conductanceof the by-pass gas line 367 to the exhaust system 318 is greater thanthe flow conductance of the vapor delivery line 340 to the depositionsystem 310, the flow rate of carrier gas can be increased in order toadjust the gas pressure in the film precursor vaporization system 350 tothe gas pressure consistent with the flow of carrier gas and filmprecursor vapor to the deposition system 310 at the deposition conditionflow rate.

The altered flow of carrier gas through the film precursor vaporizationsystem 350 is performed for a period of time sufficiently long tostabilize the gas pressure in the film precursor vaporization system 350at, for example, a pressure consistent with the deposition processconditions (i.e., the deposition condition flow rate through the filmprecursor vaporization system 350). Alternatively, the altered flow ofcarrier gas through the film precursor vaporization system 350 isperformed for a period of time sufficiently long to stabilize the gaspressure in the film precursor vaporization system 350 at, for example,a pre-determined target. A pressure measurement system may be coupled tothe film precursor vaporization system 350 in order to monitor the gaspressure and determine whether the target pressure is achieved. Theperiod of time may range from approximately 1 to approximately 30seconds and, desirably, the period of time may range from approximately1 to approximately 10 seconds; for instance, approximately 5 seconds.During this time, the substrate in the deposition system 310 is heatedand no film deposition occurs, i.e., carrier gas and precursor vapordoes not flow to the deposition system 310 by virtue of control valve342 in vapor delivery line 340 remaining in the closed position.

As illustrated in FIG. 3E, the flow of purge gas 385 from gas supplysystem 360 is continued through the purge gas line 370 to the depositionsystem 310 when control valve 372 is open, while heating of thesubstrate to the deposition temperature continues and the chamberpressure is controlled at a relatively high pressure. Once the substratetemperature reaches the elevated deposition temperature suitable forfilm deposition (approximately 200° C., as provided above), thesubstrate temperature is controlled (maintained) at the depositioncondition temperature. Additionally, once the appropriate gas pressureis achieved within the film precursor vaporization system 350 asdescribed in the preceding step, the film precursor vaporization system350 is closed (by closing the entry valve 376 and exit valve 378), and aflow of carrier gas 383 continues through by-pass valve 377 (when open)to the exhaust system 318. During this time, the deposition temperaturefor the substrate in the deposition system 310 is achieved andcontrolled, and no film deposition occurs, i.e., carrier gas andprecursor vapor does not flow to the deposition system 310 by virtue ofcontrol valve 342 in vapor delivery line 340 remaining in the closedposition.

As illustrated in FIG. 3F, an altered flow of purge gas 386 from gassupply system 360 is continued through the purge gas line 370 to thedeposition system 310 when control valve 372 is open. The flow isaltered by reducing the flow rate of purge gas in order to reduce thechamber pressure to the deposition condition. The chamber pressure mayrange from approximately 0.1 mTorr (millitorr) to approximately 200mTorr and, desirably, the chamber pressure may range from approximately1 mTorr to approximately 200 mTorr; for instance, approximately 100mTorr. Additionally, the flow of carrier gas 383 continues throughby-pass valve 377 (when open) to the exhaust system 318. During thistime, the deposition temperature for the substrate in the depositionsystem 310 is achieved and controlled, and no film deposition occurs,i.e., carrier gas and precursor vapor does not flow to the depositionsystem 310 by virtue of control valve 342 in vapor delivery line 340remaining in the closed position.

As illustrated in FIG. 3G and FIG. 4 in step 590, the temperature of thesubstrate is stabilized at the deposition temperature. The flow of purgegas 386 from gas supply system 360 is terminated, and a flow of carriergas 388 without film precursor vapor (i.e., the film precursorvaporization system 350 remains closed) is introduced to the depositionsystem 310 through vapor delivery line 340 and control valve 342 (whenopen) at the deposition condition flow rate. The flow of carrier gas 388can include the flow of carbon monoxide (CO) through flow valve 374(when open) from the third gas source 363 in the gas supply system 360,and the flow of inert gas through flow valve 375 (when open) from thefirst gas source 361 in the gas supply system 360. The chamber pressureis controlled at the deposition pressure (approximately 0.1 Torr, asprovided above).

The substrate deposition temperature can range from about 100° C. toabout 500° C. and, desirably, the substrate deposition temperature canrange from about 150° C. to about 350° C.; for instance, about 200° C.Due to the change in background gas from predominantly an inert gas,such as a noble gas (e.g., argon), to the carrier gas, which comprises acarbon monoxide (CO) component, fluctuations in substrate temperaturehave been observed. The temperature variations are believed to be causedby the difference in the thermal conductivity of the gas residingbetween the backside of the substrate and the substrate holder. Hence,the temperature variations persist for a period of time during which thecarrier gas atmosphere to be used during the deposition processdisplaces the inert gas atmosphere used during the initial heating ofthe substrate. During this time, the substrate temperature in thedeposition system 310 is controlled and no film deposition occurs, i.e.,precursor vapor does not flow to the deposition system 310 by virtue ofthe entry and exit valves 376, 378 to and from film precursorvaporization system 350 remaining in the closed position.

As illustrated in FIG. 3H and FIG. 4 in step 600, the deposition processis performed. A flow of carrier gas and film precursor vapor 389 isintroduced to the deposition system 310 through the vapor delivery line340 at the deposition condition flow rate. The flow of carrier gas caninclude the flow of carbon monoxide (CO) through flow valve 374 (whenopen) from the third gas source 363 in the gas supply system 360,through entry valve 376 (when open), through the film precursorvaporization system 350 to entrain film precursor vapor, and throughexit valve 378 (when open), and can further include the flow of inertgas through flow valve 375 (when open) from the first gas source 361 inthe gas supply system 360. The chamber pressure is controlled at thedeposition pressure (approximately 0.1 Torr, as provided above). Thesubstrate temperature is controlled at the deposition temperature(approximately 200 degrees C., as provide above). The time period forthe deposition process is chosen to be sufficiently long to affect thedeposition of a film of a desired thickness.

As would be appreciated by those skilled in the art, each of the stepsor stages in the flowchart of FIG. 4 may encompass one or more separatesteps and/or operations. Accordingly, the recitation of only ten stepsin 510, 520, 530, 540, 550, 560, 570, 580, 590, and 600 should not beunderstood to limit the method solely to ten steps or stages. Moreover,each representative step or stage 510, 520, 530, 540, 550, 560, 570,580, 590, 600 should not be understood to be limited to only a singleprocess.

FIGS. 5A through 5C schematically show formation of a metal layer on apatterned substrate according to embodiments of the invention. As thoseskilled in the art will readily appreciate, embodiments of the inventioncan be applied to patterned substrates containing one or more vias ortrenches, or combinations thereof. FIG. 5A schematically showsdeposition of a metal layer 840 onto a patterned structure 800 accordingto an embodiment of the invention. The patterned structure 800 containsa first metal layer 810, and a patterned layer 820 containing an opening830. The patterned layer 820 can, for example, be a dielectric material.The opening 830 can, for example, be a via or a trench, and the metallayer 840 can, for example, contain Ru metal.

FIG. 5B schematically shows deposition of a metal layer 860 onto apatterned structure 802 according to another embodiment of theinvention. The patterned structure 802 contains a first metal layer 810and a patterned layer 820 containing an opening 830. A barrier layer 850is deposited onto the patterned structure 802, and a metal layer 860 isdeposited on the barrier layer 850. The barrier layer 850 can, forexample, contain a tantalum-containing material (e.g., Ta, TaN, or TaCN,or a combination of two or more thereof) or a tungsten material (e.g.,W, WN). The patterned layer 820 can, for example, be a dielectricmaterial. The opening 830 can, for example, be a via or a trench, andthe metal layer 860 can, for example, contain Ru metal. FIG. 5Cschematically shows deposition of Cu in the opening 830 of FIG. 5B.

The metal layers 840 and 860 may be deposited, as described above, usinga process gas comprising a metal carbonyl precursor, for example aruthenium carbonyl, and carbon monoxide (CO). An initial flow of theprocess gas is first established for a period of time to achieve asteady flow rate before introduction to the deposition chamber. Thesteady flow of the process gas is then introduced into the chamber fordeposition of the metal layer 840 or 860 onto the patterned structure800 or 802.

Although only certain exemplary embodiments of this invention have beendescribed in detail above, those skilled in the art will readilyappreciate that many modifications are possible in the exemplaryembodiments without materially departing from the novel teachings andadvantages of this invention. Accordingly, all such modifications areintended to be included within the scope of this invention.

1. A method of depositing a thin film on a substrate, comprising:providing said substrate within a deposition system; providing a filmprecursor vaporization system coupled to said deposition system, andconfigured to supply a film precursor vapor to said deposition system;performing a deposition process within said deposition system to depositsaid thin film on said substrate by: introducing a flow of process gascontaining said film precursor vapor and a carrier gas to saidsubstrate, and maintaining said deposition system at a depositionpressure; and prior to performing said deposition process, performingthe following: heating said substrate to a deposition temperature,stabilizing said flow of process gas at a deposition flow rate withoutintroducing said flow of process gas to said deposition system,stabilizing a system pressure in said film precursor vaporization systemwithout introducing said flow of process gas to said deposition system,and stabilizing said substrate at said deposition temperature withoutintroducing said flow of process gas to said deposition system.
 2. Themethod of claim 1, wherein said stabilizing said flow of process gas atsaid deposition flow rate comprises: providing an exhaust system coupledto an outlet of said film precursor vaporization system; andestablishing a preliminary flow of process gas containing said filmprecursor vapor and said carrier gas at said deposition flow rate tosaid exhaust system.
 3. The method of claim 2, wherein said establishingsaid preliminary flow of process gas comprises: heating a film precursorto form said film precursor vapor while flowing said carrier gas over orthrough said film precursor in said film precursor vaporization system.4. The method of claim 3, wherein said film precursor comprises a metalcarbonyl precursor whereby said heating said film precursor forms ametal carbonyl precursor vapor; and wherein said flowing said carriergas over or through said film precursor comprises introducing a CO gasto said metal carbonyl precursor vapor within said film precursorvaporization system.
 5. The method of claim 1, said stabilizing saidsystem pressure in said film precursor vaporization system comprises:providing an exhaust system coupled to an outlet of said film precursorvaporization system; determining a target pressure for operating saidfilm precursor vaporization system during said deposition process;establishing a preliminary flow of process gas containing said filmprecursor vapor and said carrier gas at said deposition flow rate tosaid exhaust system; adjusting said preliminary flow of process gas tosaid exhaust system to be at a different flow rate than said depositionflow rate in order to establish a gas pressure within said filmprecursor vaporization system that is substantially equivalent to saidtarget pressure; closing said film precursor vaporization system; andterminating said preliminary flow of said process gas.
 6. The method ofclaim 1, wherein said heating said substrate comprises: contacting saidsubstrate to an upper surface of a substrate holder configured tosupport said substrate in said deposition system; providing a firstgaseous atmosphere in said deposition system; and heating said substratein said first gaseous atmosphere to said deposition temperature.
 7. Themethod of claim 6, further comprising: adjusting said first gaseousatmosphere to an elevated pressure above said deposition pressure inorder to improve a rate of said heating of said substrate; and uponheating said substrate to said deposition temperature, adjusting saidfirst gaseous atmosphere from said elevated pressure to said depositionpressure.
 8. The method of claim 7, further comprising: prior tocontacting said substrate to said substrate holder, heating saidsubstrate without contacting said substrate to said upper surface ofsaid substrate holder.
 9. The method of claim 7, wherein saidstabilizing said substrate at said deposition temperature comprises:displacing said first gaseous atmosphere with a second gaseousatmosphere; adjusting said second gaseous atmosphere to said depositionpressure; and maintaining said second gaseous atmosphere at saiddeposition pressure for a period of time, wherein the composition ofsaid second gaseous atmosphere is substantially the same as the gaseouscomposition of said deposition process.
 10. The method of claim 1,wherein said heating said substrate to said deposition temperaturecomprises heating said substrate to a temperature ranging between about50° C. and about 500° C.
 11. The method of claim 1, wherein said heatingsaid substrate to said deposition temperature comprises heating saidsubstrate to a temperature ranging between about 150° C. and about 350°C.
 12. The method of claim 1, wherein said process gas further comprisesan inert carrier gas.
 13. The method of claim 12, wherein said inertcarrier gas comprises a noble gas.
 14. The method of claim 1, whereinsaid deposition pressure is a value between about 0.1 mTorr and about200 mTorr during said exposing.
 15. The method of claim 1, wherein saidfilm precursor vapor comprises a metal carbonyl precursor vapor.
 16. Themethod of claim 15, wherein said metal carbonyl precursor vaporcomprises a tungsten carbonyl, a molybdenum carbonyl, a cobalt carbonyl,a rhodium carbonyl, a rhenium carbonyl, a chromium carbonyl, a rutheniumcarbonyl, or an osmium carbonyl, or a combination of two or morethereof.
 17. The method of claim 15, wherein said metal carbonylprecursor vapor comprises W(CO)₆, Mo(CO)₆, Co₂(CO)₈, Rh₄(CO)₁₂,Re₂(CO)₁₀, Cr(CO)₆, Ru₃(CO)₁₂, or Os₃(CO)₁₂, or a combination of two ormore thereof.
 18. The method of claim 1, wherein said carrier gascomprises an inert gas.
 19. The method of claim 1, wherein said carriergas comprises CO gas.
 20. A computer readable medium containing programinstructions for execution on a deposition system, which when executedby the deposition system, cause the deposition system to perform thesteps of: providing a substrate within said deposition system; providinga film precursor vaporization system coupled to said deposition system,and configured to supply a film precursor vapor to said depositionsystem; performing a deposition process within said deposition system todeposit a thin film on said substrate by: introducing a flow of processgas containing said film precursor vapor and a carrier gas to saidsubstrate, and maintaining said deposition system at a depositionpressure; and prior to performing said deposition process, performingthe following: heating said substrate to a deposition temperature,stabilizing said flow of process gas at a deposition flow rate withoutintroducing said flow of process gas to said deposition system,stabilizing a system pressure in said film precursor vaporization systemwithout introducing said flow of process gas to said deposition system,and stabilizing said substrate at said deposition temperature withoutintroducing said flow of process gas to said deposition system.